Stabilized grease composition containing a thiodiarylamine and a dialkyl telluride or selanide



States ING A THIODIARYLAMINE AND A DIALKYL TELLURIDE R SELANIDE HaroldA. Woods and Loren C. Bollinger, Martinez, assignors to ShellDevelopment Company, New York, N. Y., a corporation of Delaware NoDrawing. Application April 25, 1955, Serial No. 503,809

14 Claims. (Cl. 252-33.3)

This invention is concerned with improved grease compositions. Moreparticularly, it is directed to soap-base greases containing acombination of additive materials for improving the durability of thegrease.

Greases are primarily subject to the degenerating influences of air andheat. The degradation of the ingredients present in grease compositions,especially due to these two influences, results in the formation ofmaterials such as acids and the like which are corrosive to bearings andfurthermore generate additional decomposition of certain of the greaseingredients. Numerous additives have been investigated for improvingvarious properties of greases including their corrosion resistance,thermal stability, oxidation resistance and extreme pressure properties.It has been the experience of most investigators to find that theaddition of many materials, while improving the grease composition withrespect to a certain function thereof, simultaneously causes orincreases a disadvantageous property of the grease. More specifically,certain corrosion inhibitors have been found to improve the corrosionresistance of the grease compositions but at the same time to cause thelatter to have poorer oxidation (or bearing performance) properties.

As the temperature of bearing operation is elevated, the properties ofthe grease become more and more critical, since at these elevatedtemperatures, the degradation processes are accelerated. Moreover,additives which may have functioned at lower temperatures are oftenfound to reverse their behavior when the composition is utilized for thelubrication of bearings operated at temperatures in the order of 250 F.and higher.

It is an object of the present invention to provide improved greasecompositions. It is another object of this invention to provide greaseshaving improved oxidation and corrosion characteristics. It is a furtherobject of this invention to improve the oxidation (or bearingperformance) properties of the greases which have been stabilized withrespect to corrosion resistant properties. Other objects will becomeapparent during the following discussion.

Now, in accordance with the present invention, it has been found thatgreases comprising mineral oil gelled to a grease consistency with analkali metal soap are unexpectedly improved with respect to theiroperating bearing lubrication life by the combined addition thereto of athiodiarylamine and a compound of the general formula wherein R is analiphatic radical, R1 is a substituent of the group consisting ofhydrogen atoms and aliphatic radicals, X is an element of the groupconsisting of selenium and tellurium and n is a whole integer less than3, said compound containing at least 8 carbon atoms per molecule.

More particularly, it has been found that this combination of additivematerials is especially useful in alkali metal soap greases which havebeen previously stabilized against corrosion by the addition ofoil-soluble sulfonates and/ or the presence of alkylphenoxypolyethoxyethanols, Still more particularly, alkali metal soap greases containingthe combination of oil-soluble petroleum sulfonates together with thealkylphenoxypolyethoxy ethanols have been found to be improved inresistance 'to corrosiorr but their oxidation (or bearing performance)properties have been impaired by the presence of these combinedadditives. The present invention comprises the discovery that thisdisadvantageous property is unexpectedly overcome to a surprisinglygreat degree by the combined presence of the thiodiarylamines and thedialkyl selenides or tellurides (or the corresponding mercaptans). Thisis especially unexpected in view of the fact that the use of theindividual additives is of a relatively minor order but that whenemploying both of the materials together far more than an additiveefiect results.

The soaps which are utilized as the gelling agent for the subject greasecompositions comprise the alkali metal soaps of fatty or hydroxy fattyacids wherein single acids or mixtures thereof may be employed, theacids predominating in members having carbon atom chain lengths ofbetween about 12 and about 24 carbon atoms and preferably between about16 and 22 carbon atoms. The alkali metal radical may be either sodium,lithium or potassium, or mixtures thereof, while the greatest responseis found when modifying greases gelled with either soaps predominatingin lithium l2-hydroxy stearate or soaps predominating in lithiumstearate, or mixtures of said soaps. The proportion of soap utilized inthe subject composition may vary depending upon the consistency desired,but should be suflicient to gel the lubricating oil to a greaseconsistency. Normally, the soap content will'be within the range fromabout 5% to about 25% by weight of the composition.

SELENIUM AND TELLURIUM COMPOUNDS The selenium and tellurium compoundsadded for their synergistic stabilizing effect have the generalconfiguration:

wherein R is an aliphatic radical, R1 is a substituent of the groupconsisting of hydrogen atoms and aliphatic radicals, X is an element ofthe group consisting of selenium and tellurium and n is a whole numberless than 3, i. e., 1 or 2, said compound containing at least 8 carbonatoms per molecule. Preferably, the constituents R and R1 are aliphatichydrocarbon radicals and the element X is selenium. The three principalgroups of compounds falling within the general formula, as definedabove, include dialkyl selenides, dialkyl diselenides and alkylselenomercaptans as well as the analagoustellurium compounds andsubstituted or unsaturated analogs of the same. The followingdescription of specific materials meeting the above requirements definesthe classes contemplated:

1S0 Ditetradecyl selenide, is C14H29 Se C14H29iso Dihep-tadecylselenide, iso C17H35 Se C17 Has-iso Polar substituted monoselenides Bis(beta-chlorocetyl) selenide 0 Hair 0 H' C HgSe-CH:' C H- 014E ('11 $1Bis beta-hydroxy cetyl) selenide 0 H19- 0 H- C Hg-Se-CHg- C H- C Hg: 1a:H

, 3 Diselenides v v Dilauryl diselenide, n- C12Hz5-(Se)z-C12H25n Dicetyldiselenide, n--C1sHas--(Se)2-C1sHa3-n Monotellurides Dicetyl telluride,n-C1sH3aTeC1eI-I3s-n Miscellaneous selenides Diparafiin-selenidepreparedby condensing chlorinated parafiin wax with NazSe. Most probably amixture ofcompoundscorresponding to the formulaR-Se-R, where R is a.higher alkyl radical. Dilauryl= selenoxide As stated, dialkyl selenidesanddialkyl tellurides preferably containing at least'8. carbon atoms inan alkyl group, may be-employed in accordance with the invention. Thealkyl groups R and R1 may be not only straight and branched chainsaturated alkyl groups C11H21L+l, but also straight and-branched chainunsaturated aliphatic groups CnHZn-l, C71H21L3, etc., and alsocycloalkyl or cy'cloaliphatic groups. 'That is,--the1 groups attached toselenium and tellurium in the compounding agents of the presentinvention, may be saturated, unsaturated or cyclic aliphatic groups.Also, the groups R and R1 may be substituted by aromatic groups, such asthephenyl, hydroxy phenyl' and amino phenyl groups, provided such groupsare spaced at least one carbon atom from the group (X11). Polar groups,such as chlorine, bromine, hydroxyl, ether, keto, amino, free carboxyl,metallo carboxyl, carboxy ester, mercapto, mercaptide," inono-, diandpoly-sulfide, etc., may be substituted in the groups R and R1 of theselenides and tellurides of the present invention. Two or more selenideor telluride groups (X)'n may be present in the molecule.

The following specific examples of selenides and tellurides, togetherwith those specifically mentioned herein above, will illustrate theselenium and tellurium compounds of the present invention: decyl methylmenoselenide, cetyl ethyl monoselenide, octyl decyl monoselenide;dieicosyl monoselenidejdioctyl diselenide, didecyl diselenide,diheptadecyl dise'lenide, dieicosyl diselenide; decyl methylmonotelluride, cetyl ethyl monotelluride, octyl decyl monotelluridedidecyl monotelluride, diundecyl monotelluride, dilauryl monotelluride,ditetradecyl monotelluride, dicetyl monotelluride, diheptadecylmonotelluride, dieicosyl monotelluride; dioctyl ditelluride, didecylditelluride, dilauryl ditelluride, dicetyl ditelluride; and the variousmonoand poly-selenides and monoand polytellurides prepared by reactingsodium or other alkali metal monoor poly-selenides or monoorpoly-tellurides with halogenated, e. g., chlorinated hydrocarbons, suchas decyl chloride, dodecyl chloride, tetradecyl chloride, cetylchloride, heptadecyl chloride, eicosyl chloride, chlorinated lubricatingoil and chlorinated wax.

The selenides are preferred to the tellurides, because they are morestable and more easily prepared. However, the tellurides are highlyeffective as oil stabilizers and may be preferred in certain cases.Mixtures of selenides or tellurides are suitable, such as those preparedby condensing a metal selenide, polyselenide, telluride or polytelluridewith a chlorinated or brominated mixture of hydrocarbons, for example,chlorinated or brominated lubricating oil or parafiin wax. It is notessential that all of the halogen be removed in the condensationreaction; thus a chlorinecontaining dialkyl selenide ortelluride ormixture of dialkyl selenides or tellurides may be used. Also, a mixtureof selenides and tellurides may be used.

In addition to the monoaud di-selenides and their tellurium analogs,seleno-"-or' telluro-mercaptans are also effective. These seleniumcompounds arethe aliphatic selenomercaptans. Tellurium may besubstituted for selenium,

lit

although the selenium compounds are preferred. These compounds may berepresented by the formula:

wherein R1, R2 and R3 are hydrogen or organic radicals (any two of whichmay be joined to form a single, bivalent radical), C is an aliphaticcarbon atom (i. e., a carbon atom other than a carbon atom forming partof a benzenoid ring), and X is selenium or tellurium.

The preferred compounds of the invention are those containing 8 to 30carbon atoms, most advantageously, 10 to 30 carbon atoms in themolecule. As stated, the selenium compounds are preferred to thetellurium compounds.

Examples of selenium and tellurium compounds of the invention areZ-ethylhexyl, decyl, lauryl, cetyl, octadecyl, and paraflinselenomercaptans and 2-ethylhexyl, lauryl and octadecyltelluromercaptans. Other-radicals (i. e., other alkyl radicals such asundecyl and tetradecyl, aralkyl radicals such as 'cetylbenzyl andcycloaliphatic radicals such as ethylcyclohexyl and butyl cyclohexyl),may be used in place of the above-mentioned radicals, and the organicradical attached to selenium may contain an .unsaturated group or may besubstituted by a non-hydrocarbon substituent such as chlorine, hydroxyl,alkoxyl,

amino, etc.

By parafiin as used herein to designate an organic radical is meant aradical derived from paraffin wax; e. g., parafiin selenomercaptan is aselenomercaptau (actually, a mixing of selenomercaptan), such as can'beprepared by using chlorinated paraffin wax as an organic chloride, R.Cl,to be reacted, with NazSez to form a dialkyl diselenide, RSeSeR.

By aliphatic as used herein without qualification to designate anorganic radical attached to selenium or tellurium, is meant an organicradical whose attachment to selenium or tellurium is through anon-benzenoid carbon atom; e. g., octadecyl, benzyl and cyclohexylselenomercaptans are all aliphatic selenomercaptans as aliphatic isherein defined.

The second class of additives to be incorporated together with theabove-described selenides, tellurides and the corresponding mercaptanscomprise the thiodiarylamines.

Compounds of this variety have the general formula which follows:

wherein R is an aromatic radical. Three principal .classes of inhibitorsfall within the above general 'formula. These comprise species basedupon thiodiphenylamine, those based on thiophenyl naphthylamine andfinally, those based upon thiodinaphthylamine. The preferred class ofinhibitors of this type comprise the thiodiphenylamines as typified byphenothiazine. The aryl radicals contained in these materials may bemodified by such substituents as alkyl radicals having less than 6carbon atoms each, hydroxy groups or amino radicals and any aminoradicals in the compound may be likewise modified by replacement ofhydrogen atoms with alkyl, aryl, hydroxy or amino substituents. Thegeneral formulae and species thereunder of these three classes ofmaterials are given herewith:

(Based on'thiodiphenylamine) Thio-2,2'-dimethyldiphenylamineThio-4,4'-didecyldiphenylamine Thio-4,4'-dihydroxydiphenylamineThio-3,3-dibutyl diphenylamine (Based on thiophenyl naphthylamine) canThio-4-methylphenyl naphthylamine Thiophenyl-6-ethyl naphthylamineThio-4-hydroxyphenyl naphthylamine (Base on thiodinaphthylamine)Thio-di-a-naphthylamine Thio-di-fi-naphthylamine A particularlyeffective type of additive comprises the amino thiodiphenylamines whichhave the general R and R in the above formula may be substituents suchas hydrogen, alkyl, aryl, heterocyclic or cycloparaflin groups. Speciesfalling within this class are given below.

4-aminothiodiphenylamine .Z-aminothiodiphenylamine3-aminothiodiphenylamine N-acety1-2-aminothiodiphenylamineN-benzyl-2-aminothiodiphenylamine N-acetyl-4-aminothiodiphenylamineDimethyl-4-aminothiodiphenylamine The proportion of both of theseclasses of materials to be incorporated in the subject greasecompositions will vary depending upon the specific ingredients and uponthe conditions to which the compositions will be subjected. Normally,this will be between about 0.1% and about 3% by weight of the totalgrease composition. Preferably the proportions utilized are in the range0.25 to 2.5% by weight.

It has been found that it is necessary to include both of these types ofadditive materials in order to obtain the maximum bearing life. In theabsence of either of the additives, as the working examples givenhereinafter will show, the bearing life of the grease compositions isnot satisfactory. The incorporation of either of the additives in theabsence of the other somewhat increases the bearing life but still thegrease compositions do not prolong the utility of the grease to thenecessary extent.

As the working examples will demonstrate, the combination of these twomaterials produced an entirely unexpected magnitude of efiect inextending the bearing life of greases and in overcoming thedisadvantages which are created by the incorporation of other additivesutilized for special purposes. The results are especially outstandingand surprising when the additives comprise oil-soluble sulfonates oralkylphenoxypolyethoxy ethanols or combinations of these materials. AsExample I given hereinafter demonstrates, the incorporation of thelatter two materials decreases the bearing life of the grease eventhough they may at the same time provide increased protection againstcorrosion. However, the addition of phenothiazine and dilauryl selenideto these greases containing the sulfonates and ethanols resulted notonly in overcoming the degradation of the grease created by theincorporation of the two anti-corrosive materials but also,

shortened bearing life occasioned by the inclusion of sulfonates and thephenoxy ethanols in alkali metal soap greases.

The sulfonates may be oil-soluble sulfonic compounds derived from thetreatment of heavy hydrocarbon oils with strong sulfuric acid, followedby neutralization. Suitable sulfonic acids from which the salts areformed are well known in the art as possessing rust-proofing properties,and as set forth in expired U. S. Patent No. 1,630,101 granted to theStandard Oil Company of Indiana, May 24, 1927, and in other U. S.patents including Nos. 1,795,993, 2,923,367, 2,119,553, 2,182,992,2,348,715 and 2,349,785. These sulfonates contain a polar type ofmolecule which is oil-soluble, and further, they possess the property ofadhering to the metal to which they are applied, thereby preventingscufiing or pushing away of the oil films. Therefore, sulfonates keepthe metal surfaces constantly covered with a film of the lubricant andalso act as a rust-proofing agent.

Various soaps of the sulfonates may be used including metal soaps suchas sodium, lithium and calcium sulfonates. Lithium petroleum sulfonateis found to be a very satisfactory rust-proofing agent. Many of theother metal sulfonates are well known in the art to act as rustproofingagents when incorporated in a lubricating grease. However, lithiumpetroleum sulfonate, that is, the lithium soap of the product producedby reacting a lithium salt with the sulfonate resulting from thetreatment of heavy hydrocarbon oils with strong sulfuric acid, isthought to be novel with the applicants. It has also been ascertainedthat organic amino oil-soluble sulfonates function satisfactorily as arust-proofing agent when incorporated in lithium soap and sodium soapwhen the molecular weight of said sulfonates approach the molecularweight of the oil. Short chain molecules are not as soluble in oil asthe larger chain molecules. When the sulfonate derived from thetreatment of heavy hydrocarbon oils with strong sulfuric acid is treatedwith sodium hydroxide, there results a sulfonate molecule which may be amonoor disubstituted sulfonated aromatic or aliphatic molecule. Thealkali petroleum sulfonates and the synthetic hydrocarbon sulfonateswhich give the best results are those which have an average molecularWeight of 300 to 500, thereby tending to make the sulfonate quitesoluble in both naphthenic and paraffinic base oils.

The phenoxy ethanols have the general formula where R is an aromaticnucleus of the benzene, anthracene, phenanthrene, naphthalene or othercondensed ring series, Y is an aliphatic, cycloaliphatic, arylaliphaticor aryl group having at least four carbon atoms, and n is a whole numberbetween 3 and 10 (preferably 4). Representative of the compoundscontemplated for use as rust-preventive additives in greases of thisinvention are substituted phenoxy tetraethoxy ethanols, substitutednaphthoxy tetraethoxy ethanols, sub stituted anthroxy tetraethoxyethanols, substituted phenanthroxy tetraethoxy ethanols, and the like,wherein at least one of the substituents in the aromatic nucleus is agroup such as butyl, amyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl,oleyl or other alkyl group containing up to 30 carbon atoms; acycloaliphatic group, such as cyclohexyl, octyl-cyclohexyl,lauryl-cyclohexyl, cetyl-cyclohexyl, butyl-cyclohexyl, etc.; bornyl,abietyl, decahydronaphthyl, tetrahydroabietyl, or other terpenic radicalor a naphtbenic radical; phenyl, benzyl, phenylethyl, phenylisobutyl orother aryl or arylaliphatic hydrocarbon group. The substituents abovementioned may have straight or branched chains and the aromatic nucleusof the -above-defined compounds may have more than one substituent which.may' eitherbe the sameor a different group. In general, when more thanone;.s.ubstituent-;-is present in the aromatic nucleus of the abovecompounds, at least one of the substituents will contain four orrnorecarbon atoms; the remaining substituent'or substituents may thenoptionally contain less than four carbon. atoms and be represented bymethyl, ethyl, propyl, isopropyl radicals, and the like.

It has been found, as a general rule, that the. diand poly-substitutedcompounds of thetype described above are more eifective in inhibitingrustformation when. incorporated in greases than the mono-substitutedcompounds. The use of the former type compounds accordinglyrepresents apreferred embodiment of this invention. In particular, thesubstitutedphenoxy tetraethoxy ethanols. are suitably employed as rust-preventiveadditives in the greases of the present invention. Of the varioussubstituentgroups, preference is accorded those compounds containingalkyl substituents.

The above-described compounds may be suitably prepared .by condensingaphenolic compound corresponding to the formula:

with a'cornpound of the type:

H-( OCI-IzCHz) nX in which n is an integer between about 3 and 1:0,preferably 5, X is a halogen atom, said condensation taking place in thepresence of an alkali to split out an alkali metal halide and thus yieldthe desired inhibitor.

The following examples illustrate the principles of the presentinvention but are meant only to be illustrative thereof and not limitedthereto.

Example I .A grease prepared by gellinga 4:1 weight ratio ofbis(2-ethylhexyl) sebacate and light mineral lubricating oil withlithium stearate was used as the primary grease tobe modified byadditives and is labeled grease A. Grease B was formed by incorporatingin this. grease 1.5% by Weight of sodium petroleum sulfonates having anaverage molecular weight of about 470 and 1% by Weight of octyl phenoxytetraethoxy ethanol. Grease C was prepared by modifying grease B Withthe addition of 1% by weight of phenothiazine and 1% by'weight ofdilauryl selenide. The table given below lists the data obtained byutilizing these three greases in a high temperature bearing test attemperatures of 250 and 300 F. at 10,000 R. P. M.

TABLE I High High Temperature Temperature Bearing Test Bearing Test 300F., 10,000 250 F., 10,000 R. P. M., Hours R. P.'M., Hours to failure tofailure Grease A 157 1,018 Grease B 600 Grease C 1, 587

Example II A grease was prepared by gelling a medium viscosity minerallubricating oil with lithium l2-hydroxy stearate.

a The following examples illustrate typical compositions of the presentinvention.

Example. 111

Percent by weight We claim as our invention:

1. A lubricating grease comprisinga major amount of a mixed lubricatingoil, said oil comprising a major amount of bis(2-ethylhexyl) sebacateand a minor amount of a mineral oil, a minor amount of lithium stearatesufficient to thicken saidoil to a grease consistency, and 0.252% byweight each of sodium petroleum sulfonates,octylphenoxytetraethoxyethanol, dilauryl selenide and phenothiazine.

2. A lubricating grease composition comprising a major amount of amineral lubricating oil, a minor amount sufficient to gel said oil to agrease consistency, of lithium hydroxy stearate, and 0.25-2% by; weighteach of sodium petroleum sulfonates, octylphenoxytetraethoxyethanol,dilauryl selenide and phenothiazine.

3. A lubricating grease comprising a major amount of a minerallubricating oil, a minor amount of lithium stearate sufficient to gelsaid oil to a grease consistency, and from about 0.1% to about 3% -byweight each of an alkali metal hydrocarbon sulfonate, analkyl-substituted phenoxy polyethoxy ethanol,.-a dialkyl selenide and athiodiphenylamine.

4. A lubricatinggrease comprising a major amount of a mixed lubricatingoil, saidoil comprising a major amount of bis(2-e thylhexyl)sebacateandaminor amount of a mineral oil, a minor amount of lithiumstearate sufficient to thicken said oil to a grease consistency, andfrom about 0.1% to about;3% by Weight each of an alkali metalhydrocarbon'sulfonate, an alkyl-substituted phenoxy polyethoxy ethanol,a dialkyl selenide and a thiodiphenylamine.

5. A lubricating grease comprising a major amount of a mixed lubricatingoil, said oil comprising a major amount of bis(2-ethylhe,xyl) sebacateand a minor amount of a mineral oil, a minor amount of lithium stearatesufiicient to thicken said oil to a grease consistency, and from about0.1% to about 3% by weight of phenothiazine and dilauryl selenide.

6. A lubricating grease comprising a major amount of mineral lubricatingoil, a minor amount of lithium hydroxy stearate sufiicient to thickensaid-oil to a grease consistency, and from about 0.1% to about 3% byweight each of phenothiazine and dilauryl selenide.

7. A lubricatinggrease comprising a major amount of a mixed lubricatingoil, said oil comprising a major amount of .an aliphatic ester of adicarboxylic acid and a minor amountof a mineral lubricating oil, aminor amount of lithium. soaps of fatty acids sufficient to thicken saidoil to a grease consistency, and from about 0.1% ,to about 3% by Weighteach of a dialkyl selenide and a gthiodiphenylamine.

,8. A lubricating grease comprising a major amount of aminerallubricating oil, a minor amount oflithium soap of hydroxy fatty acidssuflicient to thicken the oil to a grease consistency, and from about0.1% to about 3% by weight each of a dialkyl selenide and athiodiphenylamine.

9. A lubricating grease comprising a major amount of a mixed lubricatingoil, said oil comprising a major amount of an aliphatic ester of adicarboxylic acid and a minor amount of a mineral lubricating oil, and aminor amount of a lithium soap sufficient to thicken the oil to a greaseconsistency, and from about 0.1% to about 3% by weight each of a dialkylselenide and a thiodiphenylamine.

10. A lubricating grease comprising a major amount of a lubricating oil,a minor amount of a lithium soap suflicient to thicken the oil to agrease consistency, and from about 0.1% to about 3% by weight each of adialkyl selenide and a thiodiphenylamine.

11. A lubricating grease comprising a major amount of a minerallubricating oil, a minor amount of a lithium soap sufiicient to thickenthe oil to a grease consistency, and from about 0.1% to about 3% byweight each of a dialkyl selenide and a thiodiphenylamine.

12. A lubricating grease comprising a major amount of a lubricating oil,a minor amount of an alkali metal soap sufficient to thicken the oil toa grease consistency, and from about 0.1% to about 3% by weight each ofa dialkyl selenide and a thiodiphenylamine.

wherein R is an aliphatic radical, R1 is a substituent of the groupconsisting of hydrogen atoms and aliphatic radicals, X is an element ofthe group consisting of selenium and tellurium and n is a full integerless than 3, said compound containing at least 8 carbon atoms permolecule.

References Cited in the tile of this patent UNITED STATES PATENTS2,227,908 Lewis Ian. 7, 1941 2,450,321 White et a1 Sept. 28, 19482,609,343 Saunders et a1. Sept. 2, 1952 2,652,365 Moore et a1. Sept. 15,1953 2,693,449 Hain et a1. Nov. 2, 1954

1. A LUBRICATING GREASE COMPRISING A MAJOR AMOUNT OF A MIXED LUBRICATINGOIL, SAID OIL COMPRISING A MAJOR AMOUNT OF BIS(2-ETHYLHEXYL) SEBACATEAND A MINOR AMOUNT OF A MINERAL OIL, A MINOR AMOUNT OF LITHIUM STEARATESUFFICIENT TO THICKEN SAID OIL TO A GREASE CONSISTENCY, AND 0.25-2% BYWEIGHT EACH OF SODIUM PETROLEUM SULFONATES,OCTYLPHENOXYTETRAETHOXYETHANOL, DILAURYL SELENIDE AND PHENOTHIAZINE.